CN113161601B - Electrochemical device and electronic device including the same - Google Patents
Electrochemical device and electronic device including the same Download PDFInfo
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- CN113161601B CN113161601B CN202110199799.1A CN202110199799A CN113161601B CN 113161601 B CN113161601 B CN 113161601B CN 202110199799 A CN202110199799 A CN 202110199799A CN 113161601 B CN113161601 B CN 113161601B
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- Prior art keywords
- electrolyte
- electrochemical device
- negative electrode
- carbonate
- oxide
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
An electrochemical device and an electronic device including the same are disclosed. The electrochemical device comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a negative current collector and a negative active material layer arranged on at least one surface of the negative current collector, the negative active material layer contains silicon materials, the electrolyte contains fluoroethylene carbonate, and the electrochemical device satisfies the following relational expression: 0.014 ≤ X/(Y × 2 × Z) ≤ 1.28, wherein X represents the weight percentage of fluoroethylene carbonate in the electrolyte, and 5% ≤ X ≤ 30%, and Y represents mg/cm 2 The weight of the negative electrode active material layer per unit area of one surface is calculated, Y is more than or equal to 1.95 and less than or equal to 11.69, and Z represents the weight percentage of silicon material in the negative electrode active material layer. The electrochemical device provided by the application has longer cycle life and good storage performance.
Description
Technical Field
The present application relates to an electrochemical device and an electronic device including the same.
Background
Electrochemical devices (e.g., lithium ion batteries) have excellent high temperature storage properties, high energy density, and long cycle life, and have become the most promising new green chemical power source in the world today. With the trend of lithium ion batteries to be lighter and smaller, further development of lithium batteries having high capacity density is required. The silicon material has larger lithium storage capacity and abundant content in the earth, and is an ideal negative electrode material of a lithium ion battery.
The silicon material is used as the negative electrode of the lithium ion battery, in the charge and discharge cycle process of the battery, the reversible generation and decomposition of the Li-Si alloy are accompanied with huge volume change, the SEI is continuously damaged, the pulverization or the crack of the alloy is caused, the collapse of the silicon material structure and the peeling of the electrode material are caused, the electrode material loses the electric contact, the cycle performance of the silicon negative electrode lithium ion battery is rapidly reduced, and simultaneously, the electrolyte is consumed due to the fact that the SEI needs to be continuously repaired, side reactions are increased, a large amount of gas can be generated in the charge and discharge process, and the internal gas expansion of the battery is easy to cause.
Disclosure of Invention
In a first aspect, the present application provides an electrochemical device comprising a positive electrode, a negative electrode, a separator, and an electrolyte, the negative electrode comprising a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer comprising a silicon material, the electrolyte comprising fluoroethylene carbonate, the electrochemical device satisfying the following relationship: 0.014 ≤ X/(Y × 2 × Z) ≦ 1.28, wherein X represents the weight percentage of fluoroethylene carbonate in the electrolyte, and 5% ≦ X ≦ 30%, and Y represents mg/cm 2 The weight of the negative electrode active material layer per unit area of one surface is calculated, Y is more than or equal to 1.95 and less than or equal to 11.69, and Z represents the weight percentage of silicon material in the negative electrode active material layer.
According to some embodiments of the present application, Z is 1% ≦ 90%.
According to some embodiments of the present application, Z is 5% ≦ 60%.
According to some embodiments of the present application, the electrolyte further comprises a non-fluorinated cyclic carbonate and a chain carbonate, wherein the non-fluorinated cyclic carbonate is present in an amount of 5 to 50% by weight based on the total amount of the non-fluorinated cyclic carbonate and the chain carbonate. Within this range, the lithium ion dissociation property of the electrolyte is maintained at a high level.
According to some embodiments of the present application, the electrolyte further comprises a polynitrile compound satisfying at least one of conditions (a) to (c): (a) The polynitrile compound accounts for 0.1 to 6 percent of the electrolyte in percentage by weight; (b) the polynitrile compound comprises a compound of formula II:
wherein R is 21 、R 22 、R 23 And R 24 Each independently selected from hydrogen, cyano, C 1 -C 10 Alkyl, cyano-containing C 1 -C 10 Alkyl or C containing cyano groups 1 -C 10 Ether group, R 21 、R 22 、R 23 And R 24 The total number of the contained cyano groups is more than two; (c) The polynitrile compound comprises 1,2,3-tris- (2-cyanoethoxy) propane, 1,3,6-hexanetrinitrile, adiponitrile, succinonitrile, ethylene glycol bis (ethylene glycol),
According to some embodiments of the present application, the electrolyte further comprises a boron-containing lithium salt, and the weight percentage of the boron-containing lithium salt in the electrolyte is a, the boron-containing lithium salt satisfying at least one of conditions (d) to (f):
(d) A is more than 0.1 percent and less than 1.5 percent; (e) 0.002 < A/Z < 1.5 between said A and said Z; (f) The boron-containing lithium salt compound comprises or is selected from at least one of the following:
the introduction of the boron-containing lithium salt can preferentially form a film to protect the positive electrode and the negative electrode, thereby improving the cycle stability of the electrochemical device. According to some preferred embodiments of the invention, 0.002 < A/Z < 1.5 is satisfied between A and Z.
According to some embodiments of the present application, the electrolyte further comprises a cyclic ether, and the cyclic ether accounts for 0.4% < B < 1% by weight of the electrolyte.
According to some embodiments of the invention, 0.004 < B/Z < 1 is satisfied between B and Z.
According to some embodiments of the present application, the silicon material comprises silicon oxide, elemental silicon, or a mixture of both. According to some embodiments of the present application, the Dv50 of the silicon material ranges from 2.5 μm to 20 μm.
According to some embodiments of the present application, the silicon material has an oxide coating on at least a portion of a surface thereof, wherein the oxide coating comprises at least one of an aluminum oxide, a titanium oxide, a manganese oxide, a vanadium oxide, a silicon oxide, a chromium oxide, a zirconium oxide, or a cobalt oxide.
According to some embodiments of the application, the oxide coating has a thickness of 2nm to 1000nm.
In a second aspect, the present application also provides an electronic device comprising an electrochemical device according to the first aspect of the present application.
Detailed Description
Embodiments of the present application will be described in detail below.
The electrochemical device provided by the application comprises a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode comprises a negative electrode current collector and a negative electrode active material layer coated on at least one surface of the negative electrode current collector, the negative electrode active material layer contains silicon materials, the electrolyte contains fluoroethylene carbonate, and the electrochemical device satisfies the following relational expression: 0.014 ≤ X/(Y × 2 × Z) ≤ 1.28, wherein X represents the weight percentage of fluoroethylene carbonate in the electrolyte, and 5% ≤ X ≤ 30%, and Y represents mg/cm 2 The weight of the negative electrode active material layer coated on one surface of the negative electrode current collector is measured, Y is more than or equal to 1.95 and less than or equal to 11.69, and Z represents the weight percentage of the silicon material in the negative electrode active material layer.
The fluoroethylene carbonate can form an SEI film on the surface of the negative electrode, repair the SEI film in the circulation process, and prepare the weight of the negative electrode active material and the proportion of the silicon material in the active material, so that the prepared electrochemical device can give consideration to high circulation performance, high storage performance and high energy density, and has wide application prospect.
In some embodiments, 0.05 ≦ X/(Y × 2 × Z). Ltoreq.0.38. In some embodiments, X/(Y × 2 × Z) is 0.015, 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.12, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.5, 0.6, 0.8, 0.9, 1.1, or a range consisting of any two values. In some embodiments, X is 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 28%, 30%, or a range of any two values. In some embodiments, Z is 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 28%, 30%, 35%, 38%, 40%, 45%, 48%, 50%, 55%, 60%, or a range of any two values. In some embodiments, Y is 1.95, 2.0, 2.1, 2.5, 2.8, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, or a range of any two numerical values. In some embodiments, Y is 5.19 to 9.59.
According to some embodiments of the present application, the electrolyte further comprises a non-fluorinated cyclic carbonate and a chain carbonate, wherein the non-fluorinated cyclic carbonate is present in an amount of 5 to 50% by weight based on the total amount of the non-fluorinated cyclic carbonate and the chain carbonate. Within this range, the lithium ion dissociation property of the electrolyte is maintained at a high level. According to some embodiments, the non-fluorinated cyclic carbonate may be selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, γ -butyrolactone. According to some embodiments, the chain carbonate may be selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and propyl methyl carbonate.
According to some embodiments of the present application, the electrolyte further comprises a carboxylic acid ester, and the carboxylic acid ester may be selected from one or more of ethyl acetate, propyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, and propyl butyrate.
According to some embodiments of the present application, the electrolyte further comprises a polynitrile compound, the polynitrile compound being present in the electrolyte in an amount of 0.1 to 6% by weight. In some embodiments, the percentage by weight of the polynitrile compound in the electrolyte solution is 1.0%, 1.1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.8%, 2.0%, 2.5%, 3.0%, 4.0%, 5.0%, 6.0%, or any two ranges of values.
According to some embodiments of the present application, the polynitrile compound comprises a compound of formula II:
wherein R is 21 、R 22 、R 23 And R 24 Each independently selected from hydrogen, cyano, C 1 -C 10 Alkyl, cyano-containing C 1 -C 10 Alkyl or cyano-containing C 1 -C 10 Ether group, R 21 、R 22 、R 23 And R 24 The total number of cyano groups contained is two or more.
According to some embodiments of the application, the cyano-containing alkyl is- (CH) 2 ) a-CN or
Wherein a is an integer of 1 to 10, b is an integer of 0 to 10, and c is an integer of 0 to 10. According to some embodiments of the present application, the cyano-containing ether group is- (CH) 2 ) d -O-(CH 2 ) e -CN or
Wherein d is an integer of 0 to 10, e is an integer of 1 to 10, f and h are each independently an integer of 0 to 10, and g and i are each independently an integer of 1 to 10.
In the present application, an integer of 0 to 10 means 0, 1,2,3, 4, 5, 6, 7, 8, 9, 10; integers from 1 to 10 refer to 1,2,3, 4, 5, 6, 7, 8, 9, 10.
According to some embodiments of the present application, in formula II, the alkyl is C 1 -C 6 An alkyl group. According to some embodiments, the alkyl group is ethyl, propyl, butyl, pentyl, or the like.
According to some embodiments of the present application, the polynitrile compound comprises 1,2,3-tri- (2-cyanoethoxy) propane, 1,3,6-hexanetrinitrile, adiponitrile, succinonitrile,
According to some embodiments of the present application, the polynitrile compound comprises a dinitrile compound and a polynitrile compound having two or more cyano groups, the dinitrile compound comprising at least one of adiponitrile or succinonitrile, the polynitrile compound having two or more cyano groups comprising 1,2,3-tris- (2-cyanoethoxy) propane, 1,3,6-hexanetrinitrile, and succinonitrile,
According to some embodiments of the present application, the electrolyte further comprises a boron-containing lithium salt, and the weight percentage of the boron-containing lithium salt in the electrolyte is a,0.1% < a < 1.5%. According to some embodiments, a is 0.1%, 0.2%, 0.5%, 0.6%, 0.8%, 0.9%, 1.0%, 1.1%, 1.3%, 1.4%, 1.5%, or a range of any two numerical values. The introduction of the boron-containing lithium salt can preferentially form a film to protect the positive electrode and the negative electrode, thereby improving the cycle stability of the electrochemical device. According to some preferred embodiments of the present invention, a range between a and Z of 0.002 < a/Z < 1.5, such as 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.1, 0.2, 0.5, 0.7, 0.9, 1.1, 1.3, or any two of these values, is satisfied, within which the capacity retention is high.
According to some embodiments of the present application, the lithium salt comprising boron compound comprises or is selected from at least one of:
according to some embodiments, the boron-containing lithium salt comprises or is lithium difluorooxalato borate. According to some embodiments, the boron-containing lithium salt comprises or is lithium bis (oxalato) borate. The boron-containing lithium salt includes lithium difluorooxalato borate and lithium bis-oxalato borate.
According to some embodiments of the present application, the electrolyte further comprises a cyclic ether, and the cyclic ether accounts for 0.4% < B < 1% by weight of the electrolyte, for example, B is 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or any two ranges of values. According to some embodiments of the invention, B and Z satisfy 0.004 < B/Z < 1, e.g., B/Z is 0.005, 0.008, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.1, 0.2, 0.5, 0.6, 0.7, 0.8, 0.9, or a range of any two numerical compositions. The introduction of cyclic ethers enables improved storage and higher levels of capacity retention.
According to some embodiments, the cyclic ether is selected from at least one of 1,3-dioxane, 4-methyl-1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, tetrahydropyran, and tetrahydrofuran.
According to some embodiments of the present application, the silicon material comprises silicon oxide, elemental silicon, or a mixture of both. According to some embodiments of the present application, the silicon material includes nano silicon, sub silicon oxide, silicon alloy or silicon nanowire. In order to further improve the energy density and the dynamic performance of the electrochemical device, the silicon-based negative electrode material can be three, namely, elemental silicon or a composite material formed by the elemental silicon and carbon; second, silicon oxygen compound or its composite material with carbon material; and thirdly, the alloy material consists of silicon and other metal elements.
According to some embodiments of the present application, the Dv50 of the silicon material ranges from 2.5 μm to 20 μm. According to some embodiments of the present application, the average particle diameter D50 of the negative active material is 5 μm to 15 μm. When the particle size of the negative electrode active material falls within the above range, the uniformity of the negative electrode active material layer is higher, so that the influence of too small particle size on the performance of the battery due to more side reactions with the electrolyte can be avoided, and the influence of too large particle size on the performance of the battery due to the obstruction of lithium ion transmission can be avoided.
According to some embodiments of the present application, the silicon material has an oxide coating layer on at least a portion of a surface thereof, wherein the oxide coating layer comprises at least one of aluminum (Al) oxide, titanium (Ti) oxide, manganese (Mn) oxide, vanadium (V) oxide, silicon (Si) oxide, chromium (Cr) oxide, zirconium (Zr) oxide, or cobalt (Co) oxide. According to some embodiments of the application, the oxide coating has a thickness of 2nm to 1000nm. According to some embodiments, the oxide coating layer has a thickness of 100nm to 800nm. According to some embodiments, the oxide coating layer has a thickness of 200nm to 600nm.
According to an embodiment of the present application, the negative electrode further comprises a conductive layer comprising a conductive material. Non-limiting examples of the conductive material include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fibers, carbon nanotubes, graphene, etc.), metal-based materials (e.g., metal powders, metal fibers, etc., such as copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.
The negative current collector used herein may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, polymer substrates coated with conductive metals, and combinations thereof.
According to some embodiments of the present application, the electrolyte comprises a lithium salt selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethanesulfonylimide) LiN (CF) 3 SO 2 ) 2 (LiTFSI) or lithium bis (fluorosulfonyl) imide (Li (N (SO) 2 F) 2 ) At least one of the above-mentioned). According to some embodiments of the present application, the lithium salt concentration is between 0.3mol/L and 2mol/L. According to some embodiments of the present application, the lithium salt concentration is between 0.8mol/L and 1.3 mol/L.
According to some embodiments of the present application, the electrolyte further comprises at least one of an unsaturated anhydride, a cyclic sulfate, a cyclic sultone, or a sulfone-based compound. The unsaturated anhydride may be selected from at least one of succinic anhydride, maleic anhydride, and 2-methyl maleic anhydride; the cyclic sulfate can be selected from one or two of vinyl sulfate and allyl sulfate; the cyclic sultone can be selected from at least one of 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone and methylene methanedisulfonate; the sulfone may be sulfolane.
In an electrochemical device according to the present application, a positive electrode includes a positive electrode current collector and a positive electrode active material disposed on the positive electrode current collector. The specific kind of the positive electrode active material is not particularly limited and may be selected as desired.
The positive active material may be selected from lithium cobaltate (LiCoO) 2 ) Lithium nickel manganese cobalt ternary material and lithium manganate (LiMn) 2 O 4 ) Lithium nickel manganese oxide (LiNi) 0.5 Mn 1.5 O 4 ) Lithium iron phosphate (LiFePO) 4 ) And doping and/or coating modifying compounds thereof, but the present application is not limited to these materials, and other conventionally known materials that can be used as a cathode active material may be used. These positive electrode active materials may be used alone or in combination of two or more.
In some embodiments, the positive electrode active material particles have a coating layer on at least a portion of the surface thereof. The coating layer can play a role in isolating the electrolyte, can reduce side reactions between the electrolyte and the anode active material to a great extent, reduces the dissolution of transition metal, and improves the electrochemical stability of the anode active material. The coating layer can be a carbon layer, a graphene layer, an oxide layer, an inorganic salt layer or a conductive polymer layer. The oxide can be an oxide formed by one or more elements of Al, ti, mn, zr, mg, zn, ba, mo and B; the inorganic salt may be Li 2 ZrO 3 、LiNbO 3 、Li 4 Ti 5 O 12 、Li 2 TiO 3 、Li 3 VO 4 、LiSnO 3 、Li 2 SiO 3 、LiAlO 2 One or more of the above; the conductive polymer can be polypyrrole (PPy), poly 3,4-ethylenedioxythiophene (PEDOT), or Polyamide (PI).
The positive electrode current collector for the electrochemical device according to the present application may be aluminum (Al), but is not limited thereto.
The material and shape of the separator used in the electrochemical device of the present application are not particularly limited, and may be any of the techniques disclosed in the prior art. In some embodiments, the separator includes a polymer or inorganic substance or the like formed of a material stable to the electrolyte of the present application.
For example, the separator may include a substrate layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer is at least one selected from polyethylene, polypropylene, polyethylene terephthalate and polyimide. Specifically, a polypropylene porous film, a polyethylene porous film, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, or a polypropylene-polyethylene-polypropylene porous composite film can be used.
At least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer can be a polymer layer or an inorganic layer, and can also be a layer formed by mixing a polymer and an inorganic substance.
The inorganic layer includes inorganic particles selected from at least one of alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate, and a binder. The binder is at least one selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl alkoxy, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
The polymer layer comprises a polymer, and the material of the polymer is selected from at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl alkoxy, polyvinylidene fluoride and poly (vinylidene fluoride-hexafluoropropylene).
The present application further provides an electronic device comprising the electrochemical device described herein.
The electrolyte according to the present application can suppress an increase in direct current internal resistance of an electrochemical device, so that the electrochemical device manufactured thereby is suitable for electronic apparatuses or devices in various fields.
The electronic device or apparatus of the present application is not particularly limited. In some embodiments, the electronic device of the present application includes, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a cellular phone, a portable facsimile machine, a portable copier, a portable printer, a headphone, a video recorder, a liquid crystal television, a handheld cleaner, a portable CD player, a mini-disc, a transceiver, an electronic notebook, a calculator, a memory card, a portable recorder, a radio, a backup power source, a motor, an automobile, a motorcycle, a moped, a bicycle, a lighting fixture, a toy, a game machine, a clock, a power tool, a flashlight, a camera, a large household battery, a lithium ion capacitor, and the like.
For the sake of brevity, only some numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself, as a lower or upper limit, be combined with any other point or individual value or with other lower or upper limits to form ranges not explicitly recited.
In the description herein, "above" and "below" include the present numbers unless otherwise specified.
Unless otherwise indicated, terms used in the present application have well-known meanings that are commonly understood by those skilled in the art. Unless otherwise indicated, the numerical values of the parameters mentioned in the present application can be measured by various measurement methods commonly used in the art (for example, the test can be performed according to the methods given in the examples of the present application).
The list of items to which the terms "at least one of," "at least one of," or other similar terms refer can mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means a only; only B; or A and B. In another example, if items A, B and C are listed, the phrase "at least one of A, B and C" means a only; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and all of C. Item A may comprise a single component or multiple components. Item B may comprise a single component or multiple components. Item C may comprise a single component or multiple components.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
1. Battery preparation
The lithium ion batteries of the examples and comparative examples were prepared as follows:
(1) Preparation of electrolyte
At water content<In a 10ppm argon atmosphere glove box, ethylene Carbonate (EC), propylene Carbonate (PC) and diethyl carbonate (DEC) are uniformly mixed according to a certain weight ratio, and LiPF is added 6 Stirring uniformly to form a basic electrolyte, wherein LiPF 6 The concentration of (2) is 1.15mol/L. The electrolyte was set according to the following examples and comparative examples.
(2) Preparation of positive electrode
The positive electrode active material lithium cobaltate (LiCoO) 2 ) Fully stirring and mixing acetylene black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder in a proper amount of N-methylpyrrolidone (NMP) solvent according to a weight ratio of 96; and coating the slurry on an aluminum foil of a positive current collector, drying, cold-pressing and welding a tab to obtain the positive electrode.
(3) Preparation of negative electrode
The preparation process comprises the following steps: weighing a negative electrode active material (a mixture of artificial graphite and a silicon-oxygen negative electrode active material), a carbon nano tube conductive agent and a thickening agent carboxymethylcellulose sodium (CMC) in a material tank according to a certain proportion, premixing for 30min, then adding an adhesive (styrene butadiene rubber (SBR) water emulsion with the concentration of 50% and half of polyacrylic acid aqueous solution with the concentration of 10%) and adding a proper amount of deionized water as a solvent, mechanically mixing to prepare viscous negative electrode slurry, uniformly coating the slurry on a copper foil, drying, cold-pressing and welding a tab to obtain the negative electrode.
(4) Membrane preparation
The diaphragm is Polyethylene (PE) diaphragm.
(5) Preparation of lithium ion battery
And sequentially stacking the anode, the diaphragm and the cathode to enable the diaphragm to be positioned between the anode and the cathode to play a role of isolation, then winding, placing in an outer packaging foil, injecting the prepared electrolyte into the dried battery, and carrying out vacuum packaging, standing, formation, shaping and other procedures to complete the preparation of the lithium ion battery.
2. Test method
1) Method for testing weight percentage of silicon element in negative electrode material
Taking a 5cm multiplied by 5cm area from a double-sided negative electrode active material area, scraping the material except a current collector, weighing, adding a certain amount of concentrated nitric acid for microwave digestion to obtain a solution, washing the obtained solution and filter residues for multiple times, fixing the volume to a certain volume, testing the plasma intensity of silicon in the solution through ICP-OES, and calculating the silicon content in the solution according to a standard curve of the tested elements so as to calculate the silicon content in the material; and dividing the amount of the silicon element by the weight of the cathode material to obtain the weight percentage of the silicon element in the cathode material.
2) Method for testing normal-temperature cycle performance of lithium ion battery
The lithium ion battery is placed in a thermostat with the temperature of 25 ℃, the battery is charged to 4.45V by constant current of 0.5C, the battery is charged to 0.025C by constant voltage under the voltage of 4.45V, and then the battery is discharged to 3.0V by constant current of 0.5C, and the process is marked as a charging and discharging circulation process, and the initial discharge capacity is recorded. The charge and discharge test was performed 500 times in the above manner, and the remaining discharge capacity was recorded. The capacity retention of the lithium ion battery was calculated by the following formula:
capacity retention rate = residual discharge capacity/initial discharge capacity × 100%.
3) Method for testing high-temperature storage performance of lithium ion battery
Discharging the lithium ion battery to 3.0V at 25 deg.C at 0.5C, charging to 4.45V at 0.7C, constant-voltage charging to 0.05C at 4.45V, and measuring and recording the thickness H of the lithium ion battery with micrometer 1 Placing the lithium ion battery in an oven at 80 ℃, testing and recording the thickness H of the lithium ion battery by using a micrometer after 6 hours 2 . Thickness expansion ratio = (H) 2 -H 1 )/H 1 ×100％。
3. Test results
Table 1 shows the influence of the weight percentage content X of FEC in the electrolyte, the coating weight value Y of the single-side unit area of the negative active material layer, and the weight percentage content Z of the silicon material in the negative active material on the expansion rate and capacity retention rate of the lithium ion battery stored at 80 ℃ for 6 h. In each of the examples and comparative examples shown in table 1, the weight ratio of Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC) was 1. The total amount of cyclic carbonates (EC and PC) was 30% based on the total weight of the carbonates. A negative electrode active material silicon material (Dv 50=5 μm, based on the total weight of the negative electrode active material layer, the mass ratio of the conductive agent is 1.5%, the mass ratio of the thickener is 0.5%, and the mass ratio of the binder is 2%.
TABLE 1
As shown in Table 1, comparative example 1 did not satisfy 0.014. Ltoreq. X/(Y X2 XZ). Ltoreq.1.28, and the capacity retention rate was poor. Comparative examples 2 and 3 satisfied 0.014. Ltoreq. X/(Y X2 XZ). Ltoreq.1.28, but X or Y exceeded the ranges desired in the present application (i.e., 5%. Ltoreq. X.ltoreq.30% and 1.95. Ltoreq. Y.ltoreq.11.69), the capacity retention ratio of the lithium ion battery was not effectively improved. Examples 1 to 15 not only satisfied 0.014. Ltoreq. X/(Y.times.2XZ). Ltoreq.1.28, but also 5%. Ltoreq. X.ltoreq.30% and 1.95. Ltoreq. Y.ltoreq.11.65, so that the capacity retention rate of the lithium ion battery was significantly improved.
As shown in examples 1 to 4, when Y is gradually decreased in the range of 11.69 to 1.95, the capacity retention rate of the lithium ion battery is slightly decreased, because Z is changed along with the decrease of the coating weight value CW (i.e., Y) per unit area of the single side of the negative electrode in the same capacity range when the relationship between X, Y and Z is constant. When the content of FEC in the electrolyte is too high (e.g., X =40% in comparative example 2), the content of the solvent corresponding to the electrolyte decreases, and dissociation of the lithium salt in the electrolyte is difficult; meanwhile, FEC is easy to decompose, the formation of HF in electrolyte is accelerated, the acidity of the electrolyte is increased, HF attacks the interface of the positive electrode, the dissolution of transition metal is accelerated, the performance of the battery is damaged, and the capacity retention rate of the lithium ion battery is reduced. As shown in examples 5-8 and 9-11, when Z was gradually decreased in the range of 1% to 90% or Y was gradually decreased, the capacity retention rate of the lithium ion battery was gradually increased and the expansion rate was gradually decreased at 80 ℃ storage for 6h, because the FEC content corresponding to the Si negative electrode material per unit area was increased when the Si content or the coating weight per unit area was decreased. The volume of the Si negative electrode is expanded in the circulation process, the SEI film is easy to damage, the circulation performance is deteriorated, the FEC can be reduced on the surface of the negative electrode to form a stable passivation film in advance of a solvent, the damaged SEI can be repaired in the circulation process, the damage of the SEI film in the circulation process is relieved, and meanwhile, the consumption of electrolyte in the lithium ion battery is reduced. Thereby, the capacity retention rate of the lithium ion battery is significantly improved.
As shown in examples 12 to 15, when X is gradually increased in the range of 5% to 30%, the capacity retention rate of the lithium ion battery gradually increases, and the expansion rate gradually increases after storage at 80 ℃ for 6 h. The reason is that the FEC is unstable at high temperature and is easy to generate side reaction, so that the expansion rate in the storage process is increased, and the increase of the FEC content enhances the SEI repair capability in the cycle process, so that the capacity retention rate of the lithium ion battery is increased.
Table 2 shows the effect of the total amount and proportion of cyclic carbonates (EC and PC) on the capacity retention of lithium ion batteries. The examples shown in table 2 are based on a further modification of example 1, i.e. differ only by the parameters in table 2, the EC, PC, DEC contents in table 2 being calculated on the total weight of the solvent system.
TABLE 2
As shown in examples 16 to 22, as EC PC varies in the range of 0.2 to 2, the capacity retention of the lithium ion battery is affected, and the storage expansion ratio is affected as the EC content varies. The EC reduction potential is high, so that the EC reduction potential is easy to participate in film forming on a negative electrode, the film forming reaction is increased along with the increase of the content of the EC reduction potential, and the EC reduction potential is easy to decompose and generate gas in the storage and circulation processes, so that the capacity retention rate is reduced, and the expansion rate of the battery is increased. When the EC: when the PC is between 0.3 and 1, the lithium ion battery not only has higher dissociation capability, but also can keep higher capacity retention rate and lower storage expansion rate.
As shown in examples 23 to 24, although EC: the PC is in the range of 0.3-1, but since the sum of EC and PC is more than 50%, the overall viscosity of the electrolyte is high, and ion dissociation and migration are affected, so that the capacity retention rate is at a low level.
Table 3 shows the effect of polynitrile additives on the swelling rate and capacity retention rate of lithium ion battery stored at 80 ℃ for 6h, the shown examples are improvements on the basis of example 1, i.e. only differ by the parameters in table 3, and the content of dinitrile and polynitrile compound with more than two cyano groups in table 3 is calculated based on the total weight of the electrolyte.
TABLE 3
As shown in examples 25 to 30, as the total amount of nitriles is varied in the range of 0.5 to 6%, the stabilizing ability of the polynitrile compound to the positive electrode is gradually enhanced, and thus the storage expansion rate of the lithium ion battery is gradually decreased. As shown in example 31, when the total amount of polynitrile compounds reaches 8%, the storage expansion ratio is low, but the capacity retention rate is remarkably deteriorated. This is because when the total polynitrile content is low, the interface of the positive electrode cannot be effectively protected, and the transition metal ions are dissolved out during storage, and the structure of the positive electrode material collapses, affecting the storage expansion rate. The viscosity of the polynitrile compound is high, when the content of the polynitrile compound is increased, the conductivity of the electrolyte is reduced, the impedance is increased, and the excessive polynitrile compound is easily reduced at the active site of the negative electrode to form an unstable SEI film, so that the capacity retention rate is reduced. Therefore, the content of polynitrile needs to be controlled within a certain range, and dinitrile and polynitrile compound with more than two cyano groups are used together, so that on one hand, the positive electrode interface is effectively stabilized, and on the other hand, the viscosity of the electrolyte is adjusted, and a lower storage expansion rate and a better capacity retention rate can be obtained.
The effect of boron-containing lithium salts on the storage expansion rate and capacity retention of lithium ion batteries is listed in table 4. The examples shown in table 4 are modifications of example 1, i.e. differ by the parameters in table 4.
TABLE 4
As shown in examples 35 to 38, the addition of a boron-containing lithium salt is effective in improving the capacity retention. In examples 39 and 40, when a large amount of boron-containing lithium salt is added, the capacity retention rate is reduced, and the storage expansion rate at 80 ℃ is increased, because the high amount of boron-containing lithium salt increases the battery impedance, and lithium is likely to be precipitated during the cycle, so that the capacity retention rate is reduced, and the boron-containing lithium salt is likely to decompose and generate gas during the storage process, which affects the storage at 80 ℃, it can be seen from example 41 that the content of boron-containing lithium salt needs to be controlled within a certain range, and the ratio of the content of boron-containing lithium salt to the content of Si needs to be 0.002 to 1.5, so that a high capacity retention rate can be obtained.
The effect of cyclic ether content and ratio to Si content on the lithium ion battery storage expansion ratio and capacity retention is listed in table 5. The examples shown in table 5 are modifications of example 1, i.e. differ only by the parameters in table 5.
TABLE 5
As shown in examples 42 to 48, as B/Z is between 0.04 and 1, the storage expansion rate is reduced, and it can be seen from examples 49 to 51 that the content of 1,3 dioxane needs to be in a certain range, so that the storage can be improved, and the capacity retention rate can be kept at a high level.
The effect of Dv50 of the negative silicon material on the lithium ion battery storage expansion rate and capacity retention is listed in table 6. The examples shown in table 6 are modifications of example 1, i.e. differ only by the parameters in table 6.
TABLE 6
As can be seen from comparison between example 52 and examples 54 to 57 in table 6, when the Dv50 of the silicon material is less than 2.5 μm, the capacity retention of the lithium ion battery is low, and as shown in example 58, when the Dv50 of the silicon material is greater than 20 μm, the capacity retention of the lithium ion battery is low. By comparing example 52 with example 53, when Dv50 is less than 2.5 μm, X is increased, and the capacity retention rate can be improved. This is because the negative electrode silicon particles are small and are easily pulverized after coating, so that the contact surface of the negative electrode material with the electrolyte is increased, side reactions are increased, and SEI is easily broken during a cycle, thereby deteriorating the capacity retention rate. By increasing the content of FEC, SEI on the surface of the negative electrode can be repaired, and the capacity retention rate is improved.
The effect of the M oxide coating on the capacity retention of the lithium ion battery is listed in table 7. The examples shown in examples 59 to 65 are modifications on the basis of example 1, i.e. differ by the parameters in table 7. The mass ratio of Ti to Mn in examples 64 to 65 was 1:1.
TABLE 7
By comparing examples 59 to 65 in table 7 with example 1, it can be seen that the surface of the silicon material contains an oxide coating layer, wherein M includes Ti and Mn, and the capacity retention rate is better when the thickness of the coating layer is within a certain range.
The effect of the M oxide coating on the capacity retention of the lithium ion battery is listed in table 8. Example 66 to example 68 are improvements on the basis of example 28, i.e. the distinguishing features are the parameters in table 8. The mass ratio of Ti to Mn in examples 69 to 71 was 2:1.
TABLE 8
By comparing examples 66 to 71 in table 8 with example 28, it can be seen that the surface of the silicon material contains an oxide coating layer, where M includes Ti and Mn, and the thickness of the coating layer is within a certain range, the capacity retention rate is better and the high temperature storage performance is improved.
Although illustrative embodiments have been illustrated and described, it will be appreciated by those skilled in the art that the above embodiments are not to be construed as limiting the application and that changes, substitutions and alterations can be made to the embodiments without departing from the spirit, principles and scope of the application.
Claims (11)
1. An electrochemical device comprising a positive electrode, a negative electrode, a separator, and an electrolyte, the negative electrode comprising a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer comprising a silicon material, the electrolyte comprising fluoroethylene carbonate, non-fluorinated cyclic carbonate, and chain carbonate; the non-fluorinated cyclic carbonate includes ethylene carbonate and propylene carbonate;
the electrochemical device satisfies the following relationship: 0.014 ≤ X/(Y × 2 × Z) ≤ 1.28, and
the weight of the non-fluorinated cyclic carbonate accounts for 5-50% of the total mass of the non-fluorinated cyclic carbonate and the chain carbonate; the mass ratio of the ethylene carbonate to the propylene carbonate is 0.2 to 2;
wherein X represents the weight percentage of fluoroethylene carbonate in the electrolyte, and X is more than or equal to 5% and less than or equal to 30%, and Y represents the weight percentage of fluoroethylene carbonate in mg/cm 2 The weight of the negative electrode active material layer per unit area of one surface is calculated, Y is more than or equal to 1.95 and less than or equal to 11.69, and Z represents the weight percentage of silicon material in the negative electrode active material layer.
2. The electrochemical device of claim 1, wherein Z is 1% to 90%.
3. The electrochemical device of claim 1, wherein Z is 5% to 60%.
4. The electrochemical device according to claim 1, characterized in that the mass ratio of the ethylene carbonate to the propylene carbonate is 0.3 to 1.
5. The electrochemical device according to claim 1, wherein the electrolyte further comprises a polynitrile compound satisfying at least one of conditions (a) to (c):
(a) The polynitrile compound accounts for 0.5 to 6 percent of the electrolyte in percentage by weight;
(b) The polynitrile compound includes a compound of formula II:
wherein R is 21 、R 22 、R 23 And R 24 Each independently selected from hydrogen, cyano, C 1 -C 10 Alkyl, cyano-containing C 1 -C 10 Alkyl or cyano-containing C 1 -C 10 Ether group, R 21 、R 22 、R 23 And R 24 The total number of cyano groups contained is two or more;
(c) The polynitrile compound comprises 1,2,3-tris- (2-cyanoethoxy) propane, 1,3,6-hexanetrinitrile, adiponitrile, succinonitrile, ethylene glycol bis (ethylene glycol),
6. The electrochemical device according to claim 1, wherein the electrolyte further comprises a boron-containing lithium salt, the weight percentage of the boron-containing lithium salt in the electrolyte is A, and the boron-containing lithium salt satisfies at least one of the conditions (d) to (f):
(d)0.1％＜A＜1.5％；
(e) A/Z is more than 0.002 and less than 1.5 between A and Z;
(f) The boron-containing lithium salt compound comprises or is selected from at least one of the following:
7. the electrochemical device according to claim 1, wherein the electrolyte further comprises a cyclic ether, and the cyclic ether is present in the electrolyte in an amount of B,0.4% < B < 1%.
8. The electrochemical device according to claim 7, wherein 0.004 < B/Z < 1 is satisfied between B and Z.
9. The electrochemical device as claimed in claim 1, wherein the silicon material comprises silicon oxide, elemental silicon, or a mixture thereof, and the Dv50 of the silicon material is 2.5 μm to 20 μm.
10. The electrochemical device of claim 1, wherein said silicon material has an oxide coating on at least a portion of the surface thereof, wherein said oxide coating comprises at least one of aluminum oxide, titanium oxide, manganese oxide, vanadium oxide, silicon oxide, chromium oxide, zirconium oxide, or cobalt oxide; the thickness of the oxide coating layer is 2nm to 1000nm.
11. An electronic device comprising the electrochemical device of any one of claims 1-10.
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| CN114927758A (en) * | 2022-05-17 | 2022-08-19 | 合肥国轩高科动力能源有限公司 | Electrolyte for improving high-temperature performance of lithium ion battery and lithium ion battery |
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